Protected anode active material particles for rechargeable lithium batteries

ABSTRACT

Provided is an anode particulate for a lithium battery, the particulate comprising a polymer foam material having pores and a single or a plurality of primary particles of an anode active material embedded in or in contact with said polymer foam material, wherein said primary particles of anode active material have a total solid volume Va, and said pores have a total pore volume Vp, and the volume ratio Vp/Va is from 0.1/1.0 to 10/1.

FIELD

The present disclosure relates generally to the field of lithium batteries and, in particular, to polymer foam-assisted particulates containing anode active material particles for lithium batteries.

BACKGROUND

A unit cell or building block of a lithium-ion battery is typically composed of an anode current collector, an anode or negative electrode layer (containing an anode active material responsible for storing lithium therein, a conductive additive, and a resin binder), an electrolyte and porous separator, a cathode or positive electrode layer (containing a cathode active material responsible for storing lithium therein, a conductive additive, and a resin binder), and a separate cathode current collector. The electrolyte is in ionic contact with both the anode active material and the cathode active material. A porous separator is not required if the electrolyte is a solid-state electrolyte.

The binder in the binder layer is used to bond the anode active material (e.g. graphite or Si particles) and a conductive filler (e.g. carbon black or carbon nanotube) together to form an anode layer of structural integrity, and to bond the anode layer to a separate anode current collector, which acts to collect electrons from the anode active material when the battery is discharged. In other words, in the negative electrode (anode) side of the battery, there are typically four different materials involved: an anode active material, a conductive additive, a resin binder (e.g. polyvinylidine fluoride, PVDF, or styrene-butadiene rubber, SBR), and an anode current collector (typically a sheet of Cu foil). Typically the former three materials form a separate, discrete anode layer and the latter one forms another discrete layer.

The most commonly used anode active materials for lithium-ion batteries are natural graphite and synthetic graphite (or artificial graphite) that can be intercalated with lithium and the resulting graphite intercalation compound (GIC) may be expressed as Li_(x)C₆, where x is typically less than 1. The maximum amount of lithium that can be reversibly intercalated into the interstices between graphene planes of a perfect graphite crystal corresponds to x=1, defining a theoretical specific capacity of 372 mAh/g.

Graphite or carbon anodes can have a long cycle life due to the presence of a protective solid-electrolyte interface layer (SEI), which results from the reaction between lithium and the electrolyte (or between lithium and the anode surface/edge atoms or functional groups) during the first several charge-discharge cycles. The lithium in this reaction comes from some of the lithium ions originally intended for the charge transfer purpose. As the SEI is formed, the lithium ions become part of the inert SEI layer and become irreversible, i.e. these positive ions can no longer be shuttled back and forth between the anode and the cathode during subsequent charges/discharges. Therefore, it is desirable to use a minimum amount of lithium for the formation of an effective SEI layer. In addition to SEI formation, the irreversible capacity loss Q_(ir) can also be attributed to graphite exfoliation caused by electrolyte/solvent co-intercalation and other side reactions.

In addition to carbon- or graphite-based anode materials, other inorganic materials that have been evaluated for potential anode applications include metal oxides, metal nitrides, metal sulfides, and the like, and a range of metals, metal alloys, and intermetallic compounds that can accommodate lithium atoms/ions or react with lithium. Among these materials, lithium alloys having a composition formula of Li_(a)A (A is a metal or semiconductor element, such as Al and Si, and “a” satisfies 0<a≤5) are of great interest due to their high theoretical capacity, e.g., Li₄Si (3,829 mAh/g), Li₄₄Si (4,200 mAh/g), Li₄₄Ge (1,623 mAh/g), Li₄₄Sn (993 mAh/g), Li₃Cd (715 mAh/g), Li₃Sb (660 mAh/g), Li₄₄Pb (569 mAh/g), LiZn (410 mAh/g), and Li₃Bi (385 mAh/g). However, as schematically illustrated in FIG. 2(A), in an anode composed of these high-capacity materials, severe pulverization (fragmentation of the alloy particles) occurs during the charge and discharge cycles due to severe expansion and contraction of the anode active material particles induced by the insertion and extraction of the lithium ions in and out of these particles. The expansion and contraction, and the resulting pulverization, of active material particles, lead to loss of contacts between active material particles and conductive additives and loss of contacts between the anode active material and its current collector. These adverse effects result in a significantly shortened charge-discharge cycle life.

To overcome the problems associated with such mechanical degradation, three technical approaches have been proposed:

-   (1) reducing the size of the active material particle, presumably     for the purpose of reducing the total strain energy that can be     stored in a particle, which is a driving force for crack formation     in the particle. However, a reduced particle size implies a higher     surface area available for potentially reacting with the liquid     electrolyte to form a higher amount of SEI. Such a reaction is     undesirable since it is a source of irreversible capacity loss. -   (2) depositing the electrode active material in a thin film form     directly onto a current collector, such as a copper foil. However,     such a thin film structure with an extremely small     thickness-direction dimension (typically much smaller than 500 nm,     often necessarily thinner than 100 nm) implies that only a small     amount of active material can be incorporated in an electrode (given     the same electrode or current collector surface area), providing a     low total lithium storage capacity and low lithium storage capacity     per unit electrode surface area (even though the capacity per unit     mass can be large). Such a thin film must have a thickness less than     100 nm to be more resistant to cycling-induced cracking, further     diminishing the total lithium storage capacity and the lithium     storage capacity per unit electrode surface area. Such a thin-film     battery has very limited scope of application. A desirable and     typical electrode thickness is from 100 μm to 200 μm. These     thin-film electrodes (with a thickness of <500 nm or even <100 nm)     fall short of the required thickness by three (3) orders of     magnitude, not just by a factor of 3. -   (3) using a composite composed of small electrode active particles     protected by (dispersed in or encapsulated by) a less active or     non-active matrix, e.g., carbon-coated Si particles, sol gel     graphite-protected Si, metal oxide-coated Si or Sn, and     monomer-coated Sn nano particles. Presumably, the protective matrix     provides a cushioning effect for particle expansion or shrinkage,     and prevents the electrolyte from contacting and reacting with the     electrode active material. Examples of high-capacity anode active     particles are Si, Sn, and SnO₂. Unfortunately, when an active     material particle, such as Si particle, expands (e.g. up to a volume     expansion of 380%) during the battery charge step, the protective     coating is easily broken due to the mechanical weakness and/o     brittleness of the protective coating materials. There has been no     high-strength and high-toughness material available that is itself     also lithium ion conductive.

It may be further noted that the coating or matrix materials used to protect active particles (such as Si and Sn) are carbon, sol gel graphite, metal oxide, monomer, ceramic, and lithium oxide. These protective materials are all very brittle, weak (of low strength), and/or non-conductive to lithium ions (e.g., ceramic or oxide coating). Ideally, the protective material should meet the following requirements: (a) The protective material must be lithium ion-conducting as well as initially electron-conducting (when the anode electrode is made) and be capable of preventing liquid electrolyte from being in constant contact with the anode active material particles (e.g. Si). (b) The protective material should also have high fracture toughness or high resistance to crack formation to avoid disintegration during cycling. (c) The protective material must be inert (inactive) with respect to the electrolyte, but be a good lithium ion conductor. (d) The protective material must not provide any significant amount of defect sites that irreversibly trap lithium ions. (e) The combined protective material-anode material structure must allow for an adequate amount of free space to accommodate volume expansion of the anode active material particles when lithiated. The prior art protective materials all fall short of these requirements. Hence, it was not surprising to observe that the resulting anode typically shows a reversible specific capacity much lower than expected. In many cases, the first-cycle efficiency is extremely low (mostly lower than 80% and some even lower than 60%). Furthermore, in most cases, the electrode was not capable of operating for a large number of cycles. Additionally, most of these electrodes are not high-rate capable, exhibiting unacceptably low capacity at a high discharge rate.

Due to these and other reasons, most of prior art composite electrodes and electrode active materials have deficiencies in some ways, e.g., in most cases, less than satisfactory reversible capacity, poor cycling stability, high irreversible capacity, ineffectiveness in reducing the internal stress or strain during the lithium ion insertion and extraction steps, and other undesirable side effects.

Complex composite particles of particular interest are a mixture of separate Si and graphite particles dispersed in a carbon matrix; e.g. those prepared by Mao, et al. [“Carbon-coated Silicon Particle Powder as the Anode Material for Lithium Batteries and the Method of Making the Same,” US 2005/0136330 (Jun. 23, 2005)]. Also of interest are carbon matrix-containing complex nano Si (protected by oxide) and graphite particles dispersed therein, and carbon-coated Si particles distributed on a surface of graphite particles Again, these complex composite particles led to a low specific capacity or for up to a small number of cycles only. It appears that carbon by itself is relatively weak and brittle and the presence of micron-sized graphite particles does not improve the mechanical integrity of carbon since graphite particles are themselves relatively weak. Graphite was used in these cases presumably for the purpose of improving the electrical conductivity of the anode material. Furthermore, polymeric carbon, amorphous carbon, or pre-graphitic carbon may have too many lithium-trapping sites that irreversibly capture lithium during the first few cycles, resulting in excessive irreversibility.

In summary, the prior art has not demonstrated a material that has all or most of the properties desired for use as an anode active material in a lithium-ion battery. Thus, there is an urgent and continuing need for a new anode active material that enables a lithium-ion battery to exhibit a high cycle life, high reversible capacity, low irreversible capacity, small particle sizes (for high-rate capacity), and compatibility with commonly used electrolytes. There is also a need for a method of readily or easily producing such a material in large quantities.

Thus, it is a specific object of the present disclosure to meet these needs and address the issues associated the rapid capacity decay of a lithium battery containing a high-capacity anode active material.

SUMMARY

The disclosure provides an anode particulate or multiple anode particulates for a lithium battery. The desired particulate comprises a polymer foam material having pores and a single or a plurality of primary particles of an anode active material embedded in or in contact with the polymer foam material, wherein the primary particles of anode active material have a total solid volume Va, and the pores have a total pore volume Vp, and the volume ratio Vp/Va is from 0.1/1.0 to 10/1, preferably from 0.2/1.0 to 4.0/1.0. The polymer foam may be in the form of one or a plurality of pre-made polymer foam particles having a diameter or smallest dimension from 10 nm to 20 μm. The polymer foam may be in the form of a matrix that substantially defines the particulate size and shape, wherein the primary anode active particles are dispersed. The polymer foam may have a physical density from 0.005 to 1.0 g/cm³, typically from 0.05 to 0.5 g/cm³.

In certain embodiments, the polymer foam material is selected from ethylene-vinyl acetate (EVA) foam, a copolymer of ethylene and vinyl acetate (polyethylene-vinyl acetate, PEVA), a polyethylene foam (e.g. low-density polyethylene, LDPE foam), polyimide foam, polypropylene (PP) foam, polystyrene (PS) foam (including expanded polystyrene, expanded high-impact polystyrene), polyvinyl chloride (PVC) foam; polymethacrylimide (PMI) foam, or a combination thereof.

The polymer foam material is preferably an elastomer foam having a high elasticity (recoverable deformation). Preferred examples of elastomer foams are: (a) Nitrile rubber (NBR) foam, the copolymers of acrylonitrile (ACN) and butadiene; (b) Polychloroprene foam or Neoprene; (c) Polyurethane (PU) foam (e.g. low-resilience polyurethane, memory foam, Sorbothane, and thermoplastic polyurethane foam (TPU foam)), or a combination thereof.

In some embodiments, the polymer foam material comprises a polymer selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(ethylene glycol) (PEG), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), Poly bis-methoxy ethoxyethoxide-phosphazenex, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), cyanoethyl poly(vinyl alcohol) (PVACN), aliphatic polycarbonate (including poly(vinylene carbonate) (PVC), poly(ethylene carbonate) (PEC), poly(propylene carbonate) (PPC), and poly(trimethylene carbonate) (PTMC)), single Li-ion conducting solid polymer electrolyte with a carboxylate anion, a sulfonylimide anion, or sulfonate anion, a crosslinked electrolyte of poly(ethylene glycol) diacrylate (PEGDA) or poly(ethylene glycol) methyl ether acrylate, a sulfonated derivative thereof, or a combination thereof. These polymers have not been normally or commonly made into a porous polymer or polymer foam structure for any application purpose. We have surprisingly found that these foamed polymers, in a foamed particle form implemented in the vicinity of an anode active particle or in a porous matrix form in which active particles are embedded, provide a cushioning effect against volume expansion/shrinkage of the anode active material particles and also provide lithium ion-conducting channels inside the particulate, leading to a long charge/discharge cycle life even at a relatively high charge/discharge rate (e.g. >2 C or even 5 C rate). A rate of nC means completion of a charge or discharge procedure in (1/n) hours.

In some embodiments, the anode particulate further comprises a reinforcement material selected from a carbon nanotube, carbon nano-fiber, carbon or graphite fiber, graphene sheet, expanded graphite flake, polymer fibril, glass fiber, ceramic fiber, metal filament or metal nano-wire, whisker, or a combination thereof.

In some embodiments, the anode particulate further comprises an electron-conducting material selected from expanded graphite flakes, natural graphite flakes, exfoliated graphite worms, artificial graphite particles, sol-gel graphite, carbon, carbon nanotubes, graphene sheets, or a combination thereof.

In some embodiments, the anode particulate further comprises a lithium ion-conducting additive selected from Li₂CO₃, Li₂O, Li₂C₂O₄, LiOH, LiX, ROCO₂Li, HCOLi, ROLi, (ROCO₂Li)₂, (CH₂OCO₂Li)₂, Li₂S, Li_(x)SO_(y), or a combination thereof, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, 0<x≤1, 1≤y≤4.

In some embodiments, the anode particulate further comprises a lithium ion-conducting additive selected from lithium perchlorate (LiClO₄), lithium hexafluorophosphate (LiPF₆), lithium borofluoride (LiBF₄), lithium hexafluoroarsenide (LiAsF₆), lithium trifluoro-methanesulfonate (LiCF₃SO₃), bis-trifluoromethyl sulfonylimide lithium (LiN(CF₃SO₂)₂), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF₂C₂O₄), lithium nitrate (LiNO₃), Li-fluoroalkyl-phosphate (LiPF₃(CF₂CF₃)₃), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, or a combination thereof.

In some embodiments, the anode particulate further comprises a lithium ion-conducting polymer, which is different from the polymer foam material and has a room-temperature lithium-ion conductivity from 10⁻⁸ S/cm to 5×10⁻² S/cm, more typically from 10⁻⁶ S/cm to 10⁻² S/cm.

The lithium ion-conducting polymer in the particulate may be selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(ethylene glycol) (PEG), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), Poly bis-methoxy ethoxyethoxide-phosphazenex, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), cyanoethyl poly(vinyl alcohol) (PVACN), aliphatic polycarbonate (including poly(vinylene carbonate) (PVC), poly(ethylene carbonate) (PEC), poly(propylene carbonate) (PPC), and poly(trimethylene carbonate) (PTMC)), single-ion conducting solid polymer electrolyte with a carboxylate anion, a sulfonylimide anion, or sulfonate anion, a crosslinked electrolyte of poly(ethylene glycol) diacrylate (PEGDA) or poly(ethylene glycol) methyl ether acrylate, a single-ion conducting solid polymer electrolyte of lithium bis(allylmalonato) borate (LiBAMB) and pentaerythritol tetrakis (2-mercaptoacetate) (PETMP), a sulfonated derivative thereof, or a combination thereof. For instance, a single Li-ion conducting solid polymer electrolyte may be synthesized from monomers of lithium bis (allylmalonato) borate (LiBAMB) and pentaerythritol tetrakis (2-mercaptoacetate) (PETMP) in the presence of a plasticizer, such as gamma-butyrolactone (GBL), propylene carbonate (PC) or ethylene carbonate (EC). These polymers are not generally present in a foamed polymer form inside the particulate.

In some preferred embodiments, the particulate further comprises a high-strength material, dispersed therein, selected from carbon nanotubes (single-walled or multi-walled CNTs), carbon nano-fibers (e.g. vapor-grown CNFs or carbonized electron-spun polymer nanofibers), carbon or graphite fibers, polymer fibrils (e.g. the aromatic polyamide fibrils extracted from aromatic polyamide fibers, such as Kevlar fibers), graphene sheets, expanded graphite flakes, glass fibers, ceramic fibers, metal filaments or metal nano-wires, whiskers (e.g. carbon whiskers, graphite whiskers, ceramic whiskers), or a combination thereof. An electrically conductive reinforcement is preferred.

The anode active material may be selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Nb, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; (f) prelithiated versions thereof; (g) particles of Li, Li alloy, or surface-stabilized Li having at least 60% by weight of lithium element therein; and (h) combinations thereof. The Li alloy contains mostly lithium element, but also from 0.1% to 10% by weight of a metal element selected from Zn, Ag, Au, Mg, Ni, Ti, Fe, Co, V, or a combination.

In certain embodiments, the anode active material contains a prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnO_(x), prelithiated SiO_(x), prelithiated iron oxide, prelithiated VO₂, prelithiated Co₃O₄, prelithiated Ni₃O₄, lithium titanate, or a combination thereof, wherein x=1 to 2.

The anode active material is preferably in a form of nano particle, nano wire, nano fiber, nano tube, nano sheet, nano belt, nano ribbon, nano disc, nano platelet, or nano horn having a thickness or diameter from 0.5 nm to 100 nm.

In certain embodiments, at least one of the anode active material particles is coated with a layer of carbon, intrinsically conducting conjugated polymer, or graphene prior to being encapsulated by a precursor to the carbon foam matrix.

In some embodiments, the particulate is further partially or totally encapsulated by an encapsulating shell comprising an electron-conducting material selected from a carbon, graphene, graphite, conjugated polymer, metal, or conducting composite material. Preferably, this electron-conducting material also has a lithium ion conductivity of at least 10⁻⁸ S/cm, typically up to 10⁻² S/cm.

The present disclosure also provides a powder mass of anode particulates containing the herein invented anode particulate. Also provided is a battery anode containing the invented particulate described above. The disclosure further provides a battery containing such a battery anode. The battery may be a lithium-ion battery, lithium metal secondary battery, lithium-sulfur battery, lithium-air battery, or lithium-selenium battery.

The disclosure also provides a method of producing multiple particulates containing the aforementioned anode particulate. In some embodiments, the method comprises: (a) dispersing multiple primary particles of an anode active material, having a particle size from 5 nm to 20 μm, and particles of a polymer foam material, having a particle size from 50 nm to 20 μm, plus an optional adhesive or binder, in a liquid medium to form a slurry; and (b) shaping said slurry and removing said liquid medium to form said multiple particulates having a diameter from 100 nm to 50 μm. Prior to step (a), polymer foam particles have been previously made. The slurry may further comprise a reinforcement material, an electron-conducting additive, a lithium ion-conducting additive, and/or an optional binder dispersed therein. This is illustrated in FIG. 3(A).

Step (b) may include operating a procedure selected from pan-coating, air-suspension coating, centrifugal extrusion, vibration-nozzle encapsulation, spray-drying, coacervation-phase separation, interfacial polycondensation and interfacial cross-linking, in-situ polymerization, matrix polymerization, extrusion and pelletizing, or a combination thereof.

In certain other embodiments, as illustrated in FIG. 3(B), the method comprises: (A) dispersing multiple primary particles of an anode active material, having a particle size from 5 nm to 20 μm, and reactive mass comprising a blowing agent and a polymer, reactive oligomer, or monomer with an initiator (plus an optional curing agent) in a liquid medium to form a slurry; (B) shaping the slurry and optionally removing the liquid medium to form reactive micro-droplets; and (C) polymerizing or curing the reactive micro-droplets and activating the blowing agent to produce the multiple particulates having a diameter from 100 nm to 50 μm. In some embodiments, step (A) allows primary particles of the anode active material to be substantially dispersed in the uncured polymer or reactive monomer/oligomer mass in the micro-droplets formed in step (B). Upon polymerization, curing and foaming, the anode active material particles are typically dispersed in a polymer foam matrix inside the particulate. The slurry may further comprise a reinforcement material, an electron-conducting additive, and/or a lithium ion-conducting additive dispersed therein. A curing or crosslinking agent may be used to produce a lightly crosslinked polymer or elastomer to impart a high elasticity (large, recoverable elastic deformation) to the polymer foam.

Step (B) may include operating a procedure selected from pan-coating, air-suspension coating, centrifugal extrusion, vibration-nozzle encapsulation, spray-drying, coacervation-phase separation, interfacial polycondensation and interfacial cross-linking, in-situ polymerization, matrix polymerization, extrusion and pelletizing, or a combination thereof.

The method may further comprise an encapsulating step to partially or totally encapsulate the particulate with an electron-conducting material selected from carbon, graphene, graphite, conjugated polymer, metal, or conducting composite material.

The encapsulating step may include an operation selected from physical vapor deposition, chemical vapor deposition, sputtering, polymer coating and pyrolyzation, coating of a conjugated polymer, ball-milling, spray drying, pan-coating, air-suspension coating, centrifugal extrusion, or vibration-nozzle encapsulation.

The encapsulating step may comprise operating (i) an air-jet milling procedure to embrace the particulates with natural flake graphite or (ii) a ball milling procedure to embrace the particulates with expanded graphite flakes, exfoliated graphite worms, or graphene sheets. It may be noted that expanded graphite flakes are typically produced by using mechanical shearing means (e.g. disperser machine, mechanical shearing machine, rotating-blade mixer, ultrasonicator, air jet mill, etc.) to break up the exfoliated graphite worms.

In the aforementioned methods, the ball milling operating procedure may comprise operating an apparatus selected from a vibratory ball mill, planetary ball mill, high energy mill, basket mill, agitator ball mill, cryogenic ball mill, microball mill, tumbler ball mill, continuous ball mill, stirred ball mill, pressurized ball mill, attritor, plasma-assisted ball mill, freezer mill, vibratory sieve, bead mill, nano bead mill, ultrasonic homogenizer mill, centrifugal planetary mixer, vacuum ball mill, or resonant acoustic mixer.

The method may further comprise a step of incorporating the particulates into an anode electrode of a lithium battery and a step of incorporating such an anode into a battery.

In some embodiments, the particles of anode active material contain pre-lithiated particles. In other words, before the electrode active material particles (such as Si or SnO₂) are combined with the polymer foam, these particles have been previously intercalated with Li ions (e.g. via electrochemical charging) up to an amount of 0.1% to 47% by weight of Li.

In some embodiments, prior to being combined with a polymer foam, the particles of anode active material contain primary particles pre-coated with a coating layer of a conductive material selected from carbon, pitch, carbonized resin, a conductive polymer, a conductive organic material, a metal coating, a metal oxide shell, graphene sheets, or a combination thereof. The coating layer thickness is preferably in the range from 1 nm to 20 μm, preferably from 10 nm to 10 μm, and further preferably from 100 nm to 1 μm.

In some embodiments, the particulates comprise a reinforcement material, a lithium-ion-conducting additive, or both that are dispersed therein. The reinforcement material may contain a high-strength material selected from carbon nanotubes (single-walled or multi-walled CNTs), carbon nano-fibers (e.g. vapor-grown CNFs or carbonized electron-spun polymer nanofibers), carbon or graphite fibers, polymer fibrils (e.g. the aromatic polyamide fibrils extracted from aromatic polyamide fibers, such as Kevlar fibers), graphene sheets, expanded graphite flakes, glass fibers, ceramic fibers, metal filaments or metal nano-wires, whiskers (e.g. carbon whiskers, graphite whiskers, ceramic whiskers), or a combination thereof.

The particles of anode active material may be selected from the group consisting of: (A) lithiated and un-lithiated silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (B) lithiated and un-lithiated alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (C) lithiated and un-lithiated oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Nb, Co, or Cd, and their mixtures, composites, or lithium-containing composites; (D) lithiated and un-lithiated salts and hydroxides of Sn; (E) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; and combinations thereof.

In some embodiments, the anode active material particles include powder, flakes, beads, pellets, spheres, wires, fibers, filaments, discs, ribbons, or rods, having a diameter or thickness from 2 nm to 20 μm. Preferably, the diameter or thickness is from 10 nm to 100 nm.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1(A) Schematic of a particulate comprising a polymer foam matrix, at least a primary anode material particle and a conductive additive that are dispersed in the polymer foam matrix.

FIG. 1(B) Schematic of a particulate comprising polymer foam particles, at least a primary anode material particle in contact with a polymer foam particle, and a conductive additive. An adhesive or binder (not shown) may be used to bond these ingredients together.

FIG. 2(A) Schematic illustrating the notion that expansion of Si particles, upon lithium intercalation during charging of a prior art lithium-ion battery, can lead to pulverization of Si particles, interruption of the conductive paths formed by the conductive additive, and loss of contact with the current collector;

FIG. 2(B) illustrates the issues associated with prior art anode active material; for instance, a non-lithiated Si particle encapsulated by a protective shell (e.g. carbon shell) in a core-shell structure inevitably leads to breakage of the shell and that a pre-lithiated Si particle encapsulated with a protective layer leads to poor contact between the contracted Si particle and the rigid protective shell during battery discharge.

FIG. 3(A) A diagram showing the presently invented process for producing anode particulates of FIG. 1(B), containing foamed polymer particles and anode active material particles according to an embodiment of the disclosure.

FIG. 3(B) A diagram showing the presently invented process for producing anode particulates of FIG. 1(A), containing foamed polymer matrix and anode active material particles and an electron-conducting reinforcement material dispersed in the foamed matrix according to another embodiment of the disclosure.

FIG. 3(C) Some examples of porous primary particles of an anode active material.

FIG. 4 The charge-discharge cycling behaviors of 2 lithium cells featuring Co₃O₄ particle-based anodes: one cell containing expanded graphite-embraced solid polymer-Co₃O₄ particles (substantially no pores) and the other cell containing expanded graphite-encapsulated, polymer foam-protected Co₃O₄ particles (having a pore-to-anode particle volume ratio of 1.3/1.0).

FIG. 5 The specific capacity values of 3 lithium-ion cells having SnO₂ particles as the an anode active material: one cell featuring exfoliated graphite worm-encapsulated SnO₂ particles having no pores between encapsulating exfoliated graphite worm layer and SnO₂ particles; second cell having a polymer foam between the encapsulating exfoliated graphite worm layer and SnO₂ particles with a pore-to-SnO₂ volume ration of 0.45/1.0; third cell having a polymer foam between the encapsulating graphene sheets and SnO₂ particles with a pore-to-SnO₂ volume ration of 1.25/1.0.

FIG. 6 Specific capacities of 2 lithium-ion cells having a core of Si nanowires (SiNW) embedded in an expanded graphite flake-reinforced carbon foam matrix having a pore-to-Si volume ratio of 1.85/1.0 and the other a pore-to-Si volume ratio of 0.62/1.0.

FIG. 7 Cycle life of lithium-ion cell containing expanded graphite flake-encapsulated, CNT-reinforced polymer foam protected porous Si particles, plotted as a function of the total pore-to-solid ratio in the particulate.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

A lithium-ion battery cell is typically composed of an anode current collector (e.g. Cu foil), an anode or negative electrode active material layer (i.e. anode layer typically containing particles of an anode active material, conductive additive, and binder), a porous separator and/or an electrolyte component, a cathode or positive electrode active material layer (containing a cathode active material, conductive additive, and resin binder), and a cathode current collector (e.g. Al foil). More specifically, the anode layer is composed of particles of an anode active material (e.g. graphite, Sn, SnO₂, or Si), a conductive additive (e.g. carbon black particles), and a resin binder (e.g. SBR or PVDF). This anode layer is typically 50-300 μm thick (more typically 100-200 μm) to give rise to a sufficient amount of current per unit electrode area.

In order to obtain a higher energy density cell, the anode can be designed to contain higher-capacity anode active materials having a composition formula of Li_(a)A (A is a metal or semiconductor element, such as Al and Si, and “a” satisfies 0<a≤5). These materials are of great interest due to their high theoretical capacity, e.g., Li₄Si (3,829 mAh/g), Li₄₄Si (4,200 mAh/g), Li₄₄Ge (1,623 mAh/g), Li₄₄Sn (993 mAh/g), Li₃Cd (715 mAh/g), Li₃Sb (660 mAh/g), Li₄₄Pb (569 mAh/g), LiZn (410 mAh/g), and Li₃Bi (385 mAh/g). However, as discussed in the Background section, there are several problems associated with the implementation of these high-capacity anode active materials:

-   -   1) As schematically illustrated in FIG. 2(A), in an anode         composed of these high-capacity materials, severe pulverization         (fragmentation of the alloy particles) occurs during the charge         and discharge cycles due to severe expansion and contraction of         the anode active material particles induced by the insertion and         extraction of the lithium ions in and out of these particles.         The expansion and contraction, and the resulting pulverization,         of active material particles, lead to loss of contacts between         active material particles and conductive additives and loss of         contacts between the anode active material and its current         collector. These adverse effects result in a significantly         shortened charge-discharge cycle life.     -   2) The approach of using a composite composed of small electrode         active particles protected by (dispersed in or encapsulated by)         a less active or non-active matrix, e.g., carbon-coated Si         particles, sol gel graphite-protected Si, metal oxide-coated Si         or Sn, and monomer-coated Sn nano particles, has failed to         overcome the capacity decay problem. Presumably, the protective         matrix provides a cushioning effect for particle expansion or         shrinkage, and prevents the electrolyte from contacting and         reacting with the electrode active material. Unfortunately, when         an active material particle, such as Si particle, expands (e.g.         up to a volume expansion of 380%) during the battery charge         step, the protective coating is easily broken due to the         mechanical weakness and/or brittleness of the protective coating         materials. There has been no high-strength and high-toughness         material available that is itself also lithium ion conductive.     -   3) The approach of using a core-shell structure (e.g. Si nano         particle encapsulated in a carbon or SiO₂ shell) also has not         solved the capacity decay issue. As illustrated in upper portion         of FIG. 2(B), a non-lithiated Si particle can be encapsulated by         a carbon shell to form a core-shell structure (Si core and         carbon or SiO₂ shell in this example). As the lithium-ion         battery is charged, the anode active material (carbon- or         SiO₂-encapsulated Si particle) is intercalated with lithium ions         and, hence, the Si particle expands. Due to the brittleness of         the encapsulating shell (carbon), the shell is broken into         segments, exposing the underlying Si to electrolyte and         subjecting the Si to undesirable reactions with electrolyte         during repeated charges/discharges of the battery. These         reactions continue to consume the electrolyte and reduce the         cell's ability to store lithium ions.     -   4) Referring to the lower portion of FIG. 2(B), wherein the Si         particle has been pre-lithiated with lithium ions; i.e. has been         pre-expanded in volume. When a layer of carbon (as an example of         a protective material) is encapsulated around the pre-lithiated         Si particle, another core-shell structure is formed. However,         when the battery is discharged and lithium ions are released         (de-intercalated) from the Si particle, the Si particle         contracts, leaving behind a large gap between the protective         shell and the Si particle. Such a configuration is not conducive         to lithium intercalation of the Si particle during the         subsequent battery charge cycle due to the gap and the poor         contact of Si particle with the protective shell (through which         lithium ions can diffuse). This would significantly curtail the         lithium storage capacity of the Si particle particularly under         high charge rate conditions.

In other words, there are several conflicting factors that must be considered concurrently when it comes to the design and selection of an anode active material in terms of material type, shape, size, porosity, and electrode layer thickness. Thus far, there has been no effective solution offered by any prior art teaching to these conflicting problems. We have solved these challenging issues that have troubled battery designers and electrochemists alike for more than 30 years by developing the approach of graphene-encapsulated highly porous carbon structure particulates (secondary particles) each comprising one or multiple primary particles of an anode active material dispersed in the porous carbon structure (or carbon foam). The pores in the carbon foam can accommodate the volume expansion of the primary particle(s) of the anode active material. The presence of embracing graphene sheets enables the formation of a porous carbon structure between these graphene sheets and primary anode particles (e.g. Si and SiO_(x) particles, 0<x<2.0), derived from carbonization of the polymer matrix or coating that embeds the anode primary particles. Surprisingly, without these externally wrapped graphene sheets, the polymer coating or matrix tends to form solid (relatively pore-free) carbon material when the polymer is pyrolyzed.

The disclosure provides an anode particulate or multiple anode particulates for a lithium battery. The particulate or at least one of the multiple particulates comprises a polymer foam material having pores and a single or a plurality of primary particles of an anode active material embedded in or in contact with the polymer foam material, wherein the primary particles of anode active material have a total solid volume Va, and the pores have a total pore volume Vp, and the volume ratio Vp/Va is from 0.1/1.0 to 10/1, preferably from 0.2/1.0 to 4.0/1.0.

As schematically illustrated in FIG. 1(B), the polymer foam may be in the form of one or a plurality of pre-made polymer foam particles having a particle diameter or smallest dimension from 10 nm to 20 μm, along with primary particle(s) of an anode active material and a conductive additive (e.g. carbon nanotubes, carbon nano-fibers, graphene sheets, expanded graphite sheets, conducting polymer, etc.). An adhesive or binder may be used to bond these ingredients together to form a particulate of structural integrity. Each particulate may contain therein one or a plurality of polymer foam particles.

As shown in FIG. 1(A), the polymer foam may be in the form of a matrix that substantially defines the particulate size and shape, wherein the primary anode active particles are dispersed in this polymer foam matrix. Preferably, an encapsulating shell is implemented to partially or totally embrace a particulate. Such an encapsulating shell may contain an electron-conducting material (e.g. carbon, graphene, etc.), a lithium ion-conducting material (e.g. a polymer commonly used as a solid polymer electrolyte), or a material that is both electron-conducting and ion-conducting (e.g. sulfonated conjugated polymers).

Although there is no theoretical upper limit to either the Vp/Va ratio, too large a ratio means too low an electrode packing density and, hence, a lower volumetric energy density of the resulting lithium cell. A practical upper limit for the Vp/Va ratio is 20/1.0, more preferably 10/1.0, and most preferably 5.0/1.0. A practical lower limit is 0.1/1.0, but typically >0.2/1.0, and more typically and desirably >0.3/1.0

In some preferred embodiments, the particulate is reinforced with a high-strength material selected from carbon nanotubes (single-walled or multi-walled CNTs), carbon nano-fibers (e.g. vapor-grown CNFs or carbonized electron-spun polymer nanofibers), carbon or graphite fibers, polymer fibrils (e.g. the aromatic polyamide fibrils extracted from aromatic polyamide fibers, such as Kevlar fibers), graphene sheets, expanded graphite flakes, glass fibers, ceramic fibers, metal filaments or metal nano-wires, whiskers (e.g. carbon whiskers, graphite whiskers, ceramic whiskers), or a combination thereof.

Preferably, the anode active material is a high-capacity anode active material having a specific lithium storage capacity greater than 372 mAh/g (which is the theoretical capacity of graphite).

The anode particulate may be further encapsulated by an encapsulating shell comprising an electron-conducting material (e.g. carbon, metal, conducting composite), lithium ion-conducting material (e.g. a polymer commonly used in a gel electrolyte or solid state electrolyte), and a material that is both electron-conducting and lithium-ion conducting (e.g. amorphous carbon, graphene, and conjugated polymer).

The primary anode active material particles may be porous, having surface pores or internal pores, as schematically illustrated in FIG. 3(C). The production methods of porous solid particles are well-known in the art. For instance, the production of porous Si particles may be accomplished by etching particles of a Si—Al alloy using HCl solution (to remove the Al element leaving behind pores) or by etching particles of a Si-SiO₂ mixture using HF solution (by removing SiO₂ to create pores).

Porous SnO₂ nano particles may be synthesized by a modified procedure described by Gurunathan et al [P. Gurunathan, P. M. Ette and K. Ramesha, ACS Appl. Mater. Inter., 6 (2014) 16556-16564]. In a typical synthesis procedure, 8.00 g of SnCl₂.6H₂O, 5.20 g of resorcinol and 16.0 mL of 37% formaldehyde solution were mixed in 160 mL of H₂O for about 30 minutes. Subsequently, the solution is sealed in a 250 mL round-bottom flask and kept in water bath at 80° C. for 4 hours. The resulting red gel is dried at 80° C. in an oven and calcined at 700° C. for 4 hours in N₂ and air atmosphere in sequence. Finally, the obtained white SnO₂ may be mechanically ground into finer powder for 30-60 minutes in mortar.

All types of porous anode active material particles may be produced by depositing the anode active material onto surfaces or into pores of a sacrificial material structure, followed by removing the sacrificial material. Such a deposition can be conducted using CVD, plasma-enhanced CVD, physical vapor deposition, sputtering, solution deposition, melt impregnation, chemical reaction deposition, etc.

This amount of pore volume inside the particulate (in the core portion, including the surface/internal pores of a primary particle and the pores that are not part of a primary particle) provides empty space to accommodate the volume expansion of the anode active material so that the thin encapsulating layer would not significantly expand (not to exceed 50% volume expansion of the particulate) when the lithium battery is charged. Preferably, the particulate does not increase its volume by more than 20%, further preferably less than 10% and most preferably by approximately 0% when the lithium battery is charged. This can be accomplished by making the ratio of total pore volume-to-solid anode particle volume to be in the range from 0.3/1.0 to 4.0/1.0. The total pore volume includes the pores associated with a primary particle and those pores not part of a primary particle. Such a constrained volume expansion of the particulate would not only reduce or eliminate the volume expansion of the anode electrode but also reduce or eliminate the issue of repeated formation and destruction of a solid-electrolyte interface (SEI) phase. We have discovered that this strategy surprisingly results in significantly reduced battery capacity decay rate and dramatically increased charge/discharge cycle numbers. These results are unexpected and highly significant with great utility value.

Carbon materials can assume an essentially amorphous structure (glassy carbon), a highly organized crystal (graphite), or a whole range of intermediate structures that are characterized in that various proportions and sizes of graphite crystallites and defects are dispersed in an amorphous matrix. Typically, a graphite crystallite is composed of a number of graphene sheets or basal planes that are bonded together through van der Waals forces in the c-axis direction, the direction perpendicular to the basal plane. These graphite crystallites are typically micron- or nanometer-sized. The graphite crystallites are dispersed in or connected by crystal defects or an amorphous phase in a graphite particle, which can be a graphite flake, carbon/graphite fiber segment, carbon/graphite whisker, or carbon/graphite nano-fiber. In other words, graphene planes (hexagonal lattice structure of carbon atoms) constitute a significant portion of a graphite particle.

The processes for producing exfoliated graphite worms and subsequently separated expanded graphite flakes typically involve immersing natural or artificial graphite powder in a mixture of concentrated sulfuric acid, nitric acid, and an oxidizer, such as potassium permanganate or sodium perchlorate. It typically requires 5-120 hours to complete the chemical intercalation/oxidation reaction. Once the reaction is completed, the slurry is subjected to repeated steps of rinsing and washing with water and then subjected to drying treatments to remove water. The dried powder is commonly referred to as graphite intercalation compound (GIC) or graphite oxide (GO). This GO/GIC is then subjected to a thermal shock treatment, which is most typically accomplished by exposing the GIC/GO to a furnace pre-set at a temperature of typically 800-1200° C. (more typically 950-1050° C.). This thermal shock operation typically leads to the formation of exfoliated graphite worms. A graphite worm is a bulk graphite entity that is composed of interconnected graphite flakes having large spaces between flakes. The flakes are typically composed of >100 graphene planes (>35 nm in thickness) and they are interconnected together to form a fluffy, worm-like morphology (please see the SEM image inserted in FIG. 1). When subjected to low-intensity mechanical shearing, graphite worms can be broken up into separated/isolated expanded graphite flakes. High-intensity mechanical shearing can lead to the formation of graphene sheets instead.

The disclosure also provides a method of producing multiple particulates containing the aforementioned anode particulate.

In some embodiments, as illustrated in FIG. 3(A), the method comprises: (a) dispersing multiple primary particles of an anode active material, having a particle size from 5 nm to 20 μm, and particles of a polymer foam material, having a particle size from 50 nm to 20 μm, plus an optional adhesive or binder, in a liquid medium to form a slurry; and (b) shaping said slurry and removing said liquid medium to form said multiple particulates having a diameter from 100 nm to 50 μm. Prior to step (a), polymer foam particles have been previously made. The slurry may further comprise a reinforcement material, an electron-conducting additive, a lithium ion-conducting additive, and/or an optional binder dispersed therein.

Step (b) may include operating a procedure selected from pan-coating, air-suspension coating, centrifugal extrusion, vibration-nozzle encapsulation, spray-drying, coacervation-phase separation, interfacial polycondensation and interfacial cross-linking, in-situ polymerization, matrix polymerization, extrusion and pelletizing, or a combination thereof.

In certain other embodiments, as illustrated in FIG. 3(B), the method comprises: (A) dispersing multiple primary particles of an anode active material, having a particle size from 5 nm to 20 μm, and reactive mass comprising a blowing agent and a polymer, reactive oligomer, or monomer with an initiator (plus an optional curing agent) in a liquid medium to form a slurry; (B) shaping the slurry and optionally removing the liquid medium to form reactive micro-droplets; and (C) polymerizing or curing the reactive micro-droplets and activating the blowing agent to produce the multiple particulates having a diameter from 100 nm to 50 μm. In some embodiments, step (A) allows primary particles of the anode active material to be substantially dispersed in the uncured polymer or reactive monomer/oligomer mass in the micro-droplets formed in step (B). Upon polymerization, curing and foaming, the anode active material particles are typically dispersed in a polymer foam matrix inside the particulate. The slurry may further comprise a reinforcement material, an electron-conducting additive, and/or a lithium ion-conducting additive dispersed therein. A curing or crosslinking agent may be used to produce a lightly crosslinked polymer or elastomer to impart a high elasticity (large, recoverable elastic deformation) to the polymer foam.

As will be further discussed later, step (B) may include operating a procedure selected from pan-coating, air-suspension coating, centrifugal extrusion, vibration-nozzle encapsulation, spray-drying, coacervation-phase separation, interfacial polycondensation and interfacial cross-linking, in-situ polymerization, matrix polymerization, extrusion and pelletizing, or a combination thereof to produce said multiple polymer-coated primary particles of an anode active material.

The method may further comprise an encapsulating step to partially or totally encapsulate the particulate with an electron-conducting material (selected from a carbon, graphene, expanded graphite, conjugated polymer, metal, or conducting composite material) and/or a lithium ion-conducting material (polymer for gel electrolyte or solid polymer electrolyte, sulfonated polymer, disordered carbon, etc.).

It may be noted that expanded graphite flakes are typically produced by using mechanical shearing means (e.g. disperser machine, mechanical shearing machine, rotating-blade mixer, ultrasonicator, air jet mill, etc.) to break up the exfoliated graphite worms.

Ball milling, spray-drying, suspended air coating, etc. may be used to encapsulate or embrace particulate with an encapsulating shell. In the ball milling procedure of embracing the particulates with graphene sheets, graphite worms or expanded graphite flakes, the particles of ball-milling media may be selected from ceramic particles (e.g. ZrO₂ or non-ZrO₂-based metal oxide particles), metal particles, polymer beads, glass particles, or a combination thereof.

In the aforementioned methods, the ball milling operating procedure may comprise operating an apparatus selected from a vibratory ball mill, planetary ball mill, high energy mill, basket mill, agitator ball mill, cryogenic ball mill, microball mill, tumbler ball mill, continuous ball mill, stirred ball mill, pressurized ball mill, attritor, plasma-assisted ball mill, freezer mill, vibratory sieve, bead mill, nano bead mill, ultrasonic homogenizer mill, centrifugal planetary mixer, vacuum ball mill, or resonant acoustic mixer.

A blowing agent or foaming agent is a substance which is capable of producing a cellular or foamed structure via a foaming or pore-forming process in a variety of materials that undergo hardening or phase transition, such as polymers (plastics and rubbers). Blowing agents or related pore-forming mechanisms to create pores or cells (bubbles) in a structure for producing a porous or cellular material, can be classified into the following groups:

-   -   (a) Physical blowing agents: e.g. hydrocarbons (e.g. pentane,         isopentane, cyclopentane), chlorofluorocarbons (CFCs),         hydrochlorofluorocarbons (HCFCs), and liquid CO₂. The         bubble/foam-producing process is endothermic, i.e. it needs heat         (e.g. from a melt process or the chemical exotherm due to         cross-linking), to volatize a liquid blowing agent.     -   (b) Chemical blowing agents: e.g. isocyanate, azo-, hydrazine         and other nitrogen-based materials (for thermoplastic and         elastomeric foams), sodium bicarbonate (e.g. baking soda, used         in thermoplastic foams). Here gaseous products and other         by-products are formed by a chemical reaction, promoted by         process or a reacting polymer's exothermic heat. Since the         blowing reaction involves forming low molecular weight compounds         that act as the blowing gas, additional exothermic heat is also         released. Powdered titanium hydride is used as a foaming agent         in the production of metal foams, as it decomposes to form         titanium and hydrogen gas at elevated temperatures.         Zirconium (II) hydride is used for the same purpose. Once formed         the low molecular weight compounds will never revert to the         original blowing agent(s), i.e. the reaction is irreversible.     -   (c) Mixed physical/chemical blowing agents: e.g. used to produce         flexible polyurethane (PU) foams with very low densities. Both         the chemical and physical blowing can be used in tandem to         balance each other out with respect to thermal energy         released/absorbed; hence, minimizing temperature rise. For         instance, isocyanate and water (which react to form CO₂) are         used in combination with liquid CO₂ (which boils to give gaseous         form) in the production of very low density flexible PU foams         for mattresses.     -   (d) Mechanically injected agents: Mechanically made foams         involve methods of introducing bubbles into liquid polymerizable         matrices (e.g. an unvulcanized elastomer in the form of a liquid         latex). Methods include whisking-in air or other gases or low         boiling volatile liquids in low viscosity lattices.         We have found that the above four mechanisms can all be used to         create pores in the protecting polymer.

The particulates preferably contain those anode active materials capable of storing lithium ions greater than 372 mAh/g, theoretical capacity of natural graphite. Examples of these high-capacity anode active materials are Si, Ge, Sn, SnO₂, SiO_(x), Co₃O₄, etc. As discussed earlier, these materials, if implemented in the anode, have the tendency to expand and contract when the battery is charged and discharged. At the electrode level, the expansion and contraction of the anode active material can lead to expansion and contraction of the anode, causing mechanical instability of the battery cell. At the anode active material level, repeated expansion/contraction of particles of Si, Ge, Sn, SiO_(x), SnO₂, Co₃O₄, etc. quickly leads to pulverization of these particles and rapid capacity decay of the electrode.

Thus, for the purpose of addressing these problems, the particles of solid anode active material may contain pre-lithiated particles. In other words, before the electrode active material particles (such as Si, Ge, Sn, SnO₂, Co₃O₄, etc.) are embedded in a polymer foam matrix (or combined with polymer foam particles), these particles have already been previously intercalated with Li ions (e.g. via electrochemical charging).

In some embodiments, prior to the instant particulate-forming process, the particles of anode electrode active material contain particles that have been pre-coated with a coating of a conductive material selected from carbon, pitch, carbonized resin, a conductive polymer, a conductive organic material, a graphene coating (e.g. graphene sheets), a metal coating, a metal oxide shell, or a combination thereof. The coating layer thickness is preferably in the range from 1 nm to 10 μm, preferably from 2 nm to 1 μm, and further preferably from 5 nm to 100 nm. This coating is implemented for the purpose of establishing a stable solid-electrolyte interface (SEI) to increase the useful cycle life of a lithium-ion battery.

In some embodiments, the particles of solid anode active material contain particles that are, prior to being combined with polymer foam, pre-coated with a carbon precursor material selected from a coal tar pitch, petroleum pitch, meso-phase pitch, polymer, organic material, or a combination thereof so that the carbon precursor material resides between surfaces of the solid electrode active material particles and the graphite matrix, and the method further contains a step of heat-treating the polymer-coated anode active material particles to convert the carbon precursor material to a carbon backbone material.

The same carbon precursor coating procedure may be applied to encapsulate the particulates (already containing anode active material primary particles and polymer foam). The resulting precursor-encapsulated particulates may then be heat-treated to convert the encapsulating shell into a carbon shell. The carbon material can help to completely seal off the particulate to prevent direct contact of the embraced anode active material with liquid electrolyte, which otherwise could continue to form additional SEI, thereby continuously consuming the lithium ions or solvent in the electrolyte, leading to rapid capacity decay.

In some embodiments, the method further comprises a step of exposing the particulates to CVD carbon, PVD carbon, sputtering carbon or metal oxide, or a liquid or vapor of a conductive material that is conductive to electrons and/or ions of lithium. This procedure of generating an encapsulating shell serves to provide a stable SEI or to make the SEI more stable.

The particles of anode active material may be selected from the group consisting of: (A) lithiated and un-lithiated silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (B) lithiated and un-lithiated alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (C) lithiated and un-lithiated oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Nb, Co, or Cd, and their mixtures, composites, or lithium-containing composites; (D) lithiated and un-lithiated salts and hydroxides of Sn; (E) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; and combinations thereof.

Anode active material particles and polymer foam particles (or polymer foam precursor mixture) may be made into micro-droplets and/or the micro-droplets may be encapsulated by a shell using a micro-encapsulation procedure.

Several micro-encapsulation processes require the polymer (e.g. elastomer prior to curing) to be dissolvable in a solvent. Fortunately, all the polymers used herein (as a precursor to foamed polymer or as an adhesive to bind anode particles together) are soluble in some common solvents. Even for those rubbers that are not very soluble after vulcanization, the un-cured polymer (prior to vulcanization or curing) can be readily dissolved in a common organic solvent to form a solution. Thermoplastic elastomers are also readily soluble in solvents. This solution can then be used to provide polymer-containing micro-droplets that comprise the anode active particles via several of the micro-encapsulation methods to be discussed in what follows.

There are three broad categories of micro-encapsulation methods that can be implemented to produce particulate: physical methods, physico-chemical methods, and chemical methods. The physical methods include pan-coating, air-suspension coating, centrifugal extrusion, vibration nozzle, and spray-drying methods. The physico-chemical methods include ionotropic gelation and coacervation-phase separation methods. The chemical methods include interfacial polycondensation, interfacial cross-linking, in-situ polymerization, and matrix polymerization.

Pan-Coating Method:

The pan coating process involves tumbling the active material particles (along with other ingredients, such as polymer foam particles, additive, and/or reinforcement materials) in a pan or a similar device while the encapsulating material, or matrix material, or an adhesive/binder material (e.g. elastomer monomer/oligomer, polymer melt, polymer/solvent solution, along with a blowing agent when desired) is applied slowly until a desired encapsulating shell thickness or a desired amount of matrix material or adhesive material is attained.

Air-Suspension Coating Method:

In the air suspension coating process, the solid particles (core materials, such as anode particles, foamed polymer particles, additive/reinforcement materials, etc.) are dispersed into the supporting air stream in an encapsulating chamber. A controlled stream of a polymer-solvent solution (e.g. elastomer or its monomer or oligomer dissolved in a solvent; or its monomer or oligomer alone in a liquid state) is concurrently introduced into this chamber, allowing the solution to hit and coat the suspended particles. These suspended particles are encapsulated (fully coated) with polymers while the volatile solvent is removed, leaving a thin layer of polymer (e.g. elastomer or its precursor, which is cured/hardened subsequently) on surfaces of these particles. This process may be repeated several times until the required parameters, such as full-coating thickness (i.e. encapsulating shell or wall thickness), are achieved. The air stream which supports the particles also helps to dry them, and the rate of drying is directly proportional to the temperature of the air stream, which can be adjusted for optimized shell thickness.

In a preferred mode, the particles in the encapsulating zone portion may be subjected to re-circulation for repeated coating. Preferably, the encapsulating chamber is arranged such that the particles pass upwards through the encapsulating zone, then are dispersed into slower moving air and sink back to the base of the encapsulating chamber, enabling repeated passes of the particles through the encapsulating zone until the desired encapsulating shell thickness is achieved.

Centrifugal Extrusion:

Anode active materials may be encapsulated using a rotating extrusion head containing concentric nozzles. In this process, a stream of core fluid (slurry containing particles of an anode active material and other ingredients dispersed in a solvent) is surrounded by a sheath of shell solution or melt. The suspension may also contain a conducting reinforcement material. As the device rotates and the stream moves through the air it breaks, due to Rayleigh instability, into droplets of core, each coated with the shell solution. While the droplets are in flight, the molten shell may be hardened or the solvent may be evaporated from the shell solution. If needed, the capsules can be hardened after formation by catching them in a hardening bath. Since the drops are formed by the breakup of a liquid stream, the process is only suitable for liquid or slurry. A high production rate can be achieved. Up to 22.5 kg of microcapsules can be produced per nozzle per hour and extrusion heads containing 16 nozzles are readily available.

Vibrational Nozzle Encapsulation Method:

Core-shell encapsulation or matrix-encapsulation of an anode active material (along with a reinforcement material, for instance) can be conducted using a laminar flow through a nozzle and vibration of the nozzle or the liquid. The vibration has to be done in resonance with the Rayleigh instability, leading to very uniform droplets. The liquid can consist of any liquids with limited viscosities (1-50,000 mPa·s): emulsions, suspensions or slurry containing the anode active material. The solidification can be done according to the used gelation system with an internal gelation (e.g. sol-gel processing, melt) or an external (additional binder system, e.g. in a slurry).

Spray-Drying:

Spray drying may be used to encapsulate particulates of an active material or to produce the particulates per se when desired ingredients are dissolved or suspended in a melt or polymer solution to form a suspension. The suspension may also contain anode particles, polymer foam particles, an optional reinforcement material, etc. In spray drying, the liquid feed (solution or suspension) is atomized to form droplets which, upon contacts with hot gas, allow solvent to get vaporized and thin polymer shell to fully embrace the solid particles of the active material.

Coacervation-Phase Separation:

This process consists of three steps carried out under continuous agitation:

-   (a) Formation of three immiscible chemical phases: liquid     manufacturing vehicle phase, core material phase and encapsulation     material phase. The core materials are dispersed in a solution of     the encapsulating polymer (elastomer or its monomer or oligomer).     The encapsulating material phase, which is an immiscible polymer in     liquid state, is formed by (i) changing temperature in polymer     solution, (ii) addition of salt, (iii) addition of non-solvent,     or (iv) addition of an incompatible polymer in the polymer solution. -   (b) Deposition of encapsulation shell material: core material being     dispersed in the encapsulating polymer solution, encapsulating     polymer material coated around core particles, and deposition of     liquid polymer embracing around core particles by polymer adsorbed     at the interface formed between core material and vehicle phase; and -   (c) Hardening of encapsulating shell material: shell material being     immiscible in vehicle phase and made rigid via thermal,     cross-linking, or dissolution techniques.

Interfacial Polycondensation and Interfacial Cross-Linking:

Interfacial polycondensation entails introducing the two reactants to meet at the interface where they react with each other. This is based on the concept of the Schotten-Baumann reaction between an acid chloride and a compound containing an active hydrogen atom (such as an amine or alcohol), polyester, polyurea, polyurethane, or urea-urethane condensation. Under proper conditions, thin flexible encapsulating shell (wall) forms rapidly at the interface. A solution of the anode active material and a diacid chloride are emulsified in water and an aqueous solution containing an amine and a polyfunctional isocyanate is added. A base may be added to neutralize the acid formed during the reaction. Condensed polymer shells form instantaneously at the interface of the emulsion droplets. Interfacial cross-linking is derived from interfacial polycondensation, wherein cross-linking occurs between growing polymer chains and a multi-functional chemical groups to form an elastomer shell material.

In-Situ Polymerization:

In some micro-encapsulation processes, active materials particles are fully coated with a monomer or oligomer first. Then, direct polymerization of the monomer or oligomer is carried out on the surfaces of these material particles.

Matrix Polymerization:

This method involves dispersing and embedding a core material in a polymeric matrix during formation of the particles. This can be accomplished via spray-drying, in which the particles are formed by evaporation of the solvent from the matrix material. Another possible route is the notion that the solidification of the matrix is caused by a chemical change.

Extrusion and Pelletizing:

One may simply mix anode active material particles (with or without graphene sheets or other conducting material pre-embraced around the particles) and polymer together (through blending, melt mixing, or solution mixing) to form a mixture that is extruded out of an extruder slit or spinneret holes to form rods or filaments of an anode particle-embedded polymer composite. Upon solidification, the composite rods or filaments may be cut into smaller particles using pelletizer, ball mill, etc.

In some embodiments, the anode active material particles include powder, flakes, beads, pellets, spheres, wires, fibers, filaments, discs, ribbons, or rods, having a diameter or thickness from 2 nm to 20 μm. Preferably, the diameter or thickness is from 10 nm to 100 nm.

In certain embodiments, exfoliated graphite worms and/or expanded graphite flakes, along with primary particles of an anode active material, may be mixed and charged into a chamber of an impact energy device. The energy impacting apparatus may be a vibratory ball mill, planetary ball mill, high energy mill, basket mill, agitator ball mill, cryogenic ball mill, microball mill, tumbler ball mill, continuous ball mill, stirred ball mill, pressurized ball mill, attritor, plasma-assisted ball mill, freezer mill, vibratory sieve, bead mill, nanobead mill, ultrasonic homogenizer mill, centrifugal planetary mixer, vacuum ball mill, or resonant acoustic mixer. The energy impacting apparatus may be operated to produce graphite-embraced, polymer-protected anode particles. The embracing graphite matrix in this product comprises expanded graphite flakes that are typically thicker than 35 nm, in contrast to single-layer graphene or few-layer graphene that has a thickness approximately from 0.34 nm to 3.4 nm.

The following examples serve to provide the best modes of practice for the present disclosure and should not be construed as limiting the scope of the disclosure:

Example 1: Various Blowing Agents and Pore-Forming (Bubble-Producing) Processes

In the field of plastic processing, chemical blowing agents are mixed into the plastic pellets in the form of powder or pellets and dissolved at higher temperatures. Above a certain temperature specific for blowing agent dissolution, a gaseous reaction product (usually nitrogen or CO₂) is generated, which acts as a blowing agent.

Chemical foaming agents (CFAs) can be organic or inorganic compounds that release gasses upon thermal decomposition. CFAs are typically used to obtain medium- to high-density foams, and are often used in conjunction with physical blowing agents to obtain low-density foams. CFAs can be categorized as either endothermic or exothermic, which refers to the type of decomposition they undergo. Endothermic types absorb energy and typically release carbon dioxide and moisture upon decomposition, while the exothermic types release energy and usually generate nitrogen when decomposed. The overall gas yield and pressure of gas released by exothermic foaming agents is often higher than that of endothermic types. Endothermic CFAs are generally known to decompose in the range from 130° C. to 230° C. (266-446° F.), while some of the more common exothermic foaming agents decompose around 200° C. (392° F.). However, the decomposition range of most exothermic CFAs can be reduced by addition of certain compounds. The activation (decomposition) temperatures of CFAs fall into the range of our heat treatment temperatures. Examples of suitable chemical blowing agents include sodium bi-carbonate (baking soda), hydrazine, hydrazide, azodicarbonamide (exothermic chemical blowing agents), nitroso compounds (e.g. N, N-Dinitroso pentamethylene tetramine), hydrazine derivatives (e.g. 4, 4′-Oxybis (benzenesulfonyl hydrazide) and Hydrazo dicarbonamide), and hydrogen carbonate (e.g. sodium hydrogen carbonate). These are all commercially available in plastics industry.

Technically feasible blowing agents include Carbon dioxide (CO₂), Nitrogen (N₂), Isobutane (C₄H₁₀), Cyclopentane (C₅H₁₀), Isopentane (C₅H₁₂), CFC-11 (CFCI₃), HCFC-22 (CHF₂CI), HCFC-142b (CF₂CICH₃), and HCFC-134a (CH₂FCF₃). However, in selecting a blowing agent, environmental safety is a major factor to consider. The Montreal Protocol and its influence on consequential agreements pose a great challenge for the producers of foam. Despite the effective properties and easy handling of the formerly applied chlorofluorocarbons, there was a worldwide agreement to ban these because of their ozone depletion potential (ODP). Partially halogenated chlorofluorocarbons are also not environmentally safe and therefore already forbidden in many countries. The alternatives are hydrocarbons, such as isobutane and pentane, and the gases such as CO₂ and nitrogen.

Except for those regulated substances, all the blowing agents recited above have been tested in our experiments. For both physical blowing agents and chemical blowing agents, the blowing agent amount introduced into the polymer, in terms of a blowing agent-to-polymer material weight ratio, is typically from 0/1.0 to 1.0/1.0, preferably from 0.2/1.0 to 0.8/1.0.

Example 2: Anode Particulates Comprising Expanded Graphite Flakes, Anode Particles and Polymer Foam

Several types of anode active materials in a fine powder form were investigated. These include Co₃O₄, Si, Ge, SiO_(x) (0<x<2), etc., which are used as examples to illustrate the best mode of practice. These active materials were either prepared in house or purchased from commercial sources. Primary particles of an anode active material, expanded graphite (EP) flakes, and a small but controlled amount of a blowing agent (e.g. baking soda; the proportion depending upon the porosity level desired) were dispersed in a polymer-solvent solution (e.g. Polyvinyl pyrrolidone, PVP, +water) to form a slurry, which was spray-dried to form micro-droplets. A mass of these micro-droplets containing a blowing agent was activated at approximately 150° C. to obtain anode particulates comprising anode particles and EP flakes (as an example of a conductive reinforcement material) dispersed in a porous PVP matrix.

An amount of the polymer foam-assisted particulates was then subjected to a direct transfer or indirect transfer treatment for graphene sheet encapsulation of these particulates. In a typical experiment, 1 kg of polymer foam-assisted particulates (powder), 100 grams of natural graphite flakes, and milling balls (ZrO₂ balls) were placed in a high-energy ball mill container. The high-intensity ball mill was operated at 100 rpm for 4-7 hours. The container lid was then removed and polymer foam-assisted particulates were found to be fully coated (embraced or encapsulated) with a layer of graphene sheets having a layer thickness of 0.7 nm to 3.5 nm.

Example 3: Reinforced Polymer Foam-Assisted Sn, SiO_(x), and Ge Particles

In this example, polymer foam particles were made first, and then size-reduced and combined with several different anode active materials and different reinforcement materials to form the desired particulates. Examples of the conductive reinforcement materials used in this study include graphene oxide sheets, expanded graphite flakes, and CNTs. A more desired proportion of a conductive reinforcement (reinforcement/anode active material ratio) is found to be from 2/100 to 20/100.

The polymers used in the present study were water soluble polymers, including polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), and polyacrylic acid (PAA), and the solvent used was water. In these cases, baking soda was used as a blowing agent. The selected polymer and a desired amount of baking soda (from 5/100 to 100/100 weight ratios) were dissolved in water to form a polymer solution containing up to 5% solid content. The polymer solution was then spray-dried to form micro-droplets, comprising a polymer and a blowing agent. The micro-droplets were then heated to produce polymer foam particles at a temperature above the blowing agent activation temperature and typically −20 to +10 within the melting temperature or glass transition temperature of a polymer. The polymer foam particles typically have a diameter or shortest dimension from 2 to 150 μm, which could be reduced to mostly smaller than 5 pin in size.

Polymer foam particles, primary particles of an anode active material and a reinforcement material at a desired ratio were then dispersed in a liquid medium to form a slurry, which was then spray-dried to obtain anode particulates, each containing one or a plurality of anode active particles, one or a plurality of polymer foam particles, and some amount of conductive additives (e.g. CNTs, RGO sheets, etc.).

Example 4: Exfoliated Graphite Worm-Embraced, Polymer Foam-Assisted SnO₂ Particles

Approximately 50 grams of tin oxide powder (90 nm diameter) and 5 grams of graphene sheets (available from Angstron Materials, Inc., Dayton, Ohio, USA) were then combined with a solution of thermoplastic urethane foam precursor (Sunko Chemicals Co. Taiwan) using pan-coating to obtain thermoplastic polyurethane-coated/embedded particles. The blowing agent was activated during and subsequent to the pan-coating procedure to obtain porous droplets. Airjet milling was used to further reduce the size of the droplets to approximately 4-55 μm.

Subsequently, 8 grams of the particulates, 0.6 grams of exfoliated graphite worms, and 2 grams of ZrO₂ balls were placed in a ball mill and processed for 2 hours. Typically, the particulates were embedded in exfoliated graphite worm matrix and the resulting particulates were found to be typically ellipsoidal or potato-like shape.

Example 5: Expanded Graphite Flake-Encapsulated Reinforced Carbon Foam-Protected Si Micron Particles

Cyanoethyl poly(vinyl alcohol) (PVACN) was prepared by gelation of a precursor solution, along with Si particles and graphene sheets). The precursor solution was composed of 2 wt. % PVA-CN (Shin-Etsu Chemical) dissolved in a liquid electrolyte consisting of 0.2M LiPF₆ in a liquid mixture of ethylene carbonate (EC)/dimethyl 40 carbonate (DMC)/ethylmethyl carbonate (EMC) with a volume ratio of 1:1:1. Si particles and graphene sheets were added into the solution to produce a slurry, which was spray-dried to form graphene sheet-encapsulated micro-droplets. The substantially dried precursor solution, Si particles, and some internal graphene sheets were encapsulated inside a graphene shell. These micro-droplets were then heated in a vacuum oven at a temperature of 70° C. for 2 hours to obtain black PVA-CN based porous polymer composite particulates. Si particles investigated include micron-scale Si particles (2-3 μm in diameter), sub-micron Si plates (approximately 220 nm in thickness), and Si nanowires supplied from Angstron Energy Co. (Dayton, Ohio).

Example 6: Preparation and Electrochemical Testing of Various Battery Cells

For most of the anode and cathode active materials investigated, we prepared lithium-ion cells or lithium metal cells using the conventional slurry coating method. A typical anode composition includes 85 wt. % active material (e.g., graphene-encapsulated polymer foam-protected Si or Co₃O₄ particles), 7 wt. % acetylene black (Super-P), and 8 wt. % polyvinylidene fluoride binder (PVDF, 5 wt. % solid content) dissolved in N-methyl-2-pyrrolidinoe (NMP). After coating the slurries on Cu foil, the electrodes were dried at 120° C. in vacuum for 2 h to remove the solvent. Cathode layers are made in a similar manner (using Al foil as the cathode current collector) using the conventional slurry coating and drying procedures. An anode layer, separator layer (e.g. Celgard 2400 membrane), and a cathode layer are then laminated together and housed in a plastic-Al envelop. The cell is then injected with 1 M LiPF₆ electrolyte solution dissolved in a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) (EC-DEC, 1:1 v/v). In some cells, ionic liquids were used as the liquid electrolyte. The cell assemblies were made in an argon-filled glove-box.

The cyclic voltammetry (CV) measurements were carried out using an Arbin electrochemical workstation at a typical scanning rate of 1 mV/s. In addition, the electrochemical performances of various cells were also evaluated by galvanostatic charge/discharge cycling at a current density of from 50 mA/g to 10 A/g. For long-term cycling tests, multi-channel battery testers manufactured by LAND were used.

In lithium-ion battery industry, it is a common practice to define the cycle life of a battery as the number of charge-discharge cycles that the battery suffers 20% decay in capacity based on the initial capacity measured after the required electrochemical formation.

FIG. 4 shows the charge-discharge cycling behaviors of 2 lithium cells featuring Co₃O₄ particle-based anodes: one cell containing expanded graphite-embraced solid polymer-Co₃O₄ particles (substantially no pores) and the other cell containing expanded graphite-encapsulated, polymer foam-protected Co₃O₄ particles produced by the instant method (having a pore/anode particle volume ratio of 1.2/1.0). It is clear that the presently invented graphite-encapsulated, polymer foam-protected Co₃O₄ particles exhibit significantly more stable battery cycle behavior. The cell containing graphite-encapsulated Co₃O₄ particles (no polymer foam) has a cycle life of approximately 260 cycles, at which the capacity suffers a 20% decay. In contrast, the cell featuring the EP-encapsulated, polymer foam-protected Co₃O₄ particles prepared according to the instant disclosure experiences only a 10.44% reduction in capacity after 720 cycles. Thus, the cycle life is expected to exceed 1,400 cycles. We have further observed that, in general, a higher pore-to-anode active material ratio leads to a longer cycle life until when the ratio reaches approximately 1.9/1.0 for the Co₃O₄ particle-based electrode.

Shown in FIG. 5 are the charge-discharge cycling behaviors (specific capacity) of 3 lithium-ion cells each having SnO₂ particles as the an anode active material and CNTs (5% by weight) as a conductive reinforcement: one cell featuring exfoliated graphite worm-encapsulated SnO₂ particles having no pores between encapsulating graphite worm layer and SnO₂ particles; second cell having a polymer foam between the encapsulating exfoliated graphite worms and SnO₂ particles with a pore-to-SnO₂ volume ratio of 0.45/1.0; third cell having a polymer foam between the encapsulating exfoliated graphite worms and SnO₂ particles with a pore-to-SnO₂ volume ratio of 1.25/1.0. The presently invented strategy of implementing not only embracing exfoliated graphite worms but also polymer foam connecting the graphite worms and the anode active material particles imparts a much stable cycle life to a lithium-ion battery. Again, a higher pore-to-anode active material ratio leads to a longer cycle life up to a ratio of approximately 2.2/1.0 for the SnO₂ particle-based anode.

Summarized in FIG. 6 are the specific capacities of 2 lithium-ion cells each having an amorphous carbon-encapsulated core comprising Si nanowires (SiNW) embedded in polymer foam matrix reinforced by expanded graphite flakes: one having a pore-to-Si volume ratio of 1.85/1.0 and the other a pore-to-Si volume ratio of 0.62/1.0. This result demonstrates the effectiveness of implementing an adequate amount of pores to accommodate the volume expansion of an anode active material to ensure cycling stability of a lithium-ion battery featuring a high-capacity anode active material, such as Si. We have further observed that a reinforcement material (e.g. expanded graphite flakes, graphene sheets and CNTS) in the polymer foam matrix also helps to improve the electrical conductivity and maintain the structural integrity of the polymer foam matrix against the repeated volume expansion/shrinkage of the anode active material particles.

The effects of the total pore-to-solid anode active material ratio in the invented particulates may be illustrated in FIG. 7 as an example. FIG. 7 shows the cycle life of a lithium-ion cell containing expanded graphite flake-encapsulated, CNT-reinforced polymer foam-assisted porous Si particles, plotted as a function of the total pore-to-solid ratio in the particulate. These data have demonstrated the significance of the total pore volume in impacting the cycle life of a lithium battery. Typically, there is a threshold total pore volume-to-total solid volume ratio above which a dramatic increase in cycle life is observed. 

1. An anode particulate for a lithium battery, said particulate comprising a polymer foam material having pores and a single or a plurality of primary particles of an anode active material embedded in or in contact with said polymer foam material, wherein said primary particles of anode active material have a total solid volume Va, and said pores have a total pore volume Vp, and the volume ratio Vp/Va is from 0.1/1.0 to 10/1.
 2. The anode particulate of claim 1, wherein said polymer foam material is selected from ethylene-vinyl acetate (EVA) foam, a copolymer of ethylene and vinyl acetate (polyethylene-vinyl acetate, PEVA), a polyethylene foam, polyimide foam, polypropylene (PP) foam, polystyrene (PS) foam, polyvinyl chloride (PVC) foam; polymethacrylimide (PMI) foam, or a combination thereof.
 3. The anode particulate of claim 1, wherein said polymer foam material is selected from nitrile rubber (NBR) foam, polychloroprene foam, polyurethane (PU) foam, or a combination thereof.
 4. The anode particulate of claim 1, wherein said polymer foam material comprises a polymer selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(ethylene glycol) (PEG), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), Poly bis-methoxy ethoxyethoxide-phosphazenex, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), cyanoethyl poly(vinyl alcohol) (PVACN), aliphatic polycarbonate (including poly(vinylene carbonate) (PVC), poly(ethylene carbonate) (PEC), poly(propylene carbonate) (PPC), and poly(trimethylene carbonate) (PTMC)), single Li-ion conducting solid polymer electrolyte with a carboxylate anion, a sulfonylimide anion, or sulfonate anion, a crosslinked electrolyte of poly(ethylene glycol) diacrylate (PEGDA) or poly(ethylene glycol) methyl ether acrylate, a sulfonated derivative thereof, or a combination thereof.
 5. The anode particulate of claim 1, further comprising a reinforcement material selected from a carbon nanotube, carbon nano-fiber, carbon or graphite fiber, graphene sheet, expanded graphite flake, polymer fibril, glass fiber, ceramic fiber, metal filament or metal nano-wire, whisker, or a combination thereof.
 6. The anode particulate of claim 1, further comprising an electron-conducting material selected from expanded graphite flakes, natural graphite flakes, exfoliated graphite worms, artificial graphite particles, sol-gel graphite, carbon, carbon nanotubes, graphene sheets, or a combination thereof.
 7. The anode particulate of claim 1, further comprising a lithium ion-conducting additive selected from Li₂CO₃, Li₂O, Li₂C₂O₄, LiOH, LiX, ROCO₂Li, HCOLi, ROLi, (ROCO₂Li)₂, (CH₂OCO₂Li)₂, Li₂S, Li_(x)SO_(y), or a combination thereof, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, 0<x≤1, 1≤y≤4.
 8. The anode particulate of claim 1, further comprising a lithium ion-conducting additive selected from lithium perchlorate (LiClO₄), lithium hexafluorophosphate (LiPF₆), lithium borofluoride (LiBF₄), lithium hexafluoroarsenide (LiAsF₆), lithium trifluoro-methanesulfonate (LiCF₃SO₃), bis-trifluoromethyl sulfonylimide lithium (LiN(CF₃SO₂)₂), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF₂C₂O₄), lithium nitrate (LiNO₃), Li-fluoroalkyl-phosphate (LiPF₃(CF₂CF₃)₃), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, or a combination thereof.
 9. The anode particulate of claim 1, further comprising a lithium ion-conducting polymer, which is different from the polymer foam material and has a room-temperature lithium-ion conductivity from 10⁻⁸ S/cm to 5×10⁻² S/cm.
 10. The anode particulate of claim 9, wherein said lithium ion-conducting polymer is selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(ethylene glycol) (PEG), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), poly bis-methoxy ethoxyethoxide-phosphazenex, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), cyanoethyl poly(vinyl alcohol) (PVACN), aliphatic polycarbonate (including poly(vinylene carbonate) (PVC), poly(ethylene carbonate) (PEC), poly(propylene carbonate) (PPC), and poly(trimethylene carbonate) (PTMC)), single-ion conducting solid polymer electrolyte with a carboxylate anion, a sulfonylimide anion, or sulfonate anion, a crosslinked electrolyte of poly(ethylene glycol) diacrylate (PEGDA) or poly(ethylene glycol) methyl ether acrylate, a single-ion conducting solid polymer electrolyte of lithium bis (allylmalonato) borate (LiBAMB) and pentaerythritol tetrakis (2-mercaptoacetate) (PETMP), a sulfonated derivative thereof, or a combination thereof.
 11. The anode particulate of claim 1, wherein said anode active material is selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, Nb, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; (f) prelithiated versions thereof; (g) particles of Li, Li alloy, or surface-stabilized Li having at least 60% by weight of lithium element therein; and (h) combinations thereof.
 12. The anode particulate of claim 11, wherein said Li alloy contains from 0.1% to 10% by weight of a metal element selected from Zn, Ag, Au, Mg, Ni, Ti, Fe, Co, V, or a combination.
 13. The anode particulate of claim 1, wherein said anode active material contains a prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnO_(x), prelithiated SiO_(x), prelithiated iron oxide, prelithiated VO₂, prelithiated Co₃O₄, prelithiated Ni₃O₄, lithium titanate, or a combination thereof, wherein x=1 to
 2. 14. The anode particulate of claim 1, wherein said anode active material is in a form of nano particle, nano wire, nano fiber, nano tube, nano sheet, nano belt, nano ribbon, nano disc, nano platelet, or nano horn having a thickness or diameter from 0.5 nm to 100 nm.
 15. The anode particulate of claim 1, wherein at least one of said primary particles of anode active material is coated with a layer of carbon, conducting polymer, or graphene.
 16. The anode particulate of claim 1, wherein said particulate is further partially or totally encapsulated by an electron-conducting material selected from carbon, graphene, graphite, conjugated polymer, metal, or conducting composite material.
 17. The anode particulate of claim 1, wherein the primary anode active material particles are porous, having surface pores or internal pores.
 18. A mass of anode particulates containing the anode particulate of claim
 1. 19. A battery anode containing said particulate of claim
 1. 20. A battery containing the battery anode of claim
 19. 21. The battery of claim 20, wherein said battery is a lithium-ion battery, lithium metal secondary battery, lithium-sulfur battery, lithium-air battery, or lithium-selenium battery. 